Metallized reactive naphtholazo naphthol dyestuffs containing a polyhalogenated pyrimidine group



United States Patent 3 484,431 METALLIZED REACTlVE NAPHTHOLAZO NAPH- THOL DYESTUFFS CONTAINING A POLYHALO- GEN ATED PYRIMIDIN E GROUP Lukas Schneider, Basel, Switzerland, assignor to Sandoz Ltd. (also known as Sandoz A.G.), Basel, Switzerland N0 Drawing. Continuation-impart of application Ser. No. 82,685, Jan. 16, 1961. This application July 15, 1963, Ser. No. 295,186 Claims priority, application Switzerland, Jan. 29, 1960, 984/60; Mar. 30, 1960, 3,580/60 Int. Cl. C091) 45/18 U.S. Cl. 260146 4 Claims This application is a continuation-impart of my application Ser. No. 82,685, filed Jan. 16, 1961, and now abandoned and relates to new reactive monoazo dyestuffs of the formula HOaS Y N=N-B RHN S03 (I) wherein B represents the radical of a hydroxynaphthalene or 1- aryl-S-pyrazolone which is coupled in a position vicinal to the hydroxy group, bears at least one sulfonic acid group and may contain other substituents, Y represents hydrogen or O-Cu, the copper atom being linked to the hydroxy group of the radical B in the position vicinal to -N=N and RNH- represeats a group of the formula tween 16 and 36, i.e. being chlorine or bromine,

w being hydrogen, chlorine, bromine, methyl, ethyl, carboxy or carboxymethyl,

2: being chlorine, bromine, amino, lower alkylamino,

di-(lower alkyl)-amino, lower hydroxyalkylamino, di- (lower hydroxyalkyD-amino, lower alkoxyalkylamino, lower carboxyalkylamino, N-lower alkyl-N-lower carboxyalkylamino, lower sulfoalkylamino, N-lower alkyl- N-lower sulfoalkylamino, phenylamino, N-lower alkyl- N-phenylamino, N-lower hydroxyalkyl-N-phenylamino, lower alkylphenylamino, chlorophenylamino, lower alkoxyphenylamino, carboxyphenylamino sulfophenylamino, disulfophenylamino, sulfonaphthylamino, disulfonaphthylamino, cyclohexylamino, methylcyclohexylamino, benzylamino, phenoxy or lower alkoxy, and n being one of the integers 1 and 2.

Particularly interesting dyestuffs correspond to the formulae H0 8 HO S 0- Cu-O 3,484,431 Patented Dec. 16, 1969 wherein B has the afore-cited meaning, m is one of the integers l, 2 and 3 and. R-HN corresponds to the Formula II in which w represents hydrogen, chlorine, or bromine, when n is 2, and those in which z represents amino, methylamino, 2'-hydroxyethylamino, 2.'-sulfoethylamin 3'- or 4'-sulfophenylamino, methoxy or chlorine when n is 1, and the copper complex dyestuff contains preferably a total of 4 to 5 sulfonic acid groups.

The process for their production consists in coupling 1 mol of the diazo compound of an amine of the f rmula S0311 wherein R has the afore-cited meaning,

(III) l SOaH (IV) wherein Z represents a substituent which is readily convertible into an amino group,

with 1 mol of a hydroxynaphthalene or l-aryl-S-pyrazolone bearing at least one sulfonic acid group and coupling in a position vicinal to the enolic or phenolic hydroxy group, converting the substituent. Z in the product into an amino group, condensing the resulting intermediate product with 1 mol of a polyhalogeno-triazine of the formula hal N Oha1 (IJ-N z (v) or a polyhalogeno-pyrimidine of the formula hal hal w (VI) wherein hal, z and w have the above-cited meanings, and, if desired, treating the dyestuff so formed with an oxidizing agent in presence of a copper-yielding agent.

3 N N B i=1! 114mm and Hum ($0 1+!) The following procedures can be adopted for producing the dyestuffs of the invention:

(a) 1 mol of 2,6-diamononaphthalene-4,8-disu1fonic acid is condensed with 1 mol of a compound of Formula V or VI, the intermediate thus obtained is diazotized and the diazo compound is coupled with a hydroxynaphthalene or l-aryl-S-pyrazolone bearing at least one sulfonic acid group and coupling in a position vicinal to the phenolic or enolic group and optionally the monoazo dyestuff is simultaneously oxidized and coppered;

(b) 1 mol of 2-diazonaphthalene-4.8-disulfonic acid containing in the position 6 a substituent convertible into an amino group is coupled with a hydroxynaphthalene or l-aryl-S-pyrazolone bearing at least one sulfouic acid group and coupling in a position vicinal to the phenolic or enolic group and the substituent in the position 6 of the resulting monoazo dye'stufl is converted into the amino group, this amino group is condensed with a compound of Formula V or VI and optionally the monoazo dyestuff is simultaneously oxidized and coppered;

(c) 1 mol of 2-diazonaphthalene-4.8-disulfonic acid containing in the position 6 an acylamino group is coupled with a hydroxynaphthalene or l-aryl-S-pyrazolone bearing at least one sulfonic acid group and coupling in a position vicinal to the phenolic r enolic group, the monoazo dyestulf is simultaneously oxidized and coppered, the acylamino group converted into the amino group by alkaline saponification, the copper complex meanwhile remaining intact, and the aminoazo dyestuff obtained condensed with a compound of Formula V or VI.

The compounds of Formula V are e.g. cyanuric chloride, cyanuric bromide, primary condensation products of a cyanuric halide of the composition hal- 0 wherein hal represents chlorine or bromine, and v the radical,

which may be further substituted, of a primary or secondary aliphatic, alicyclic, aromatic or heterocyclic amine, an aliphatic, alicyclic, aromatic or heterocyclic hydroxyor thiol compound, in particular the radical of aniline, its alkyl and sulfonic acid or carboxylic acid derivatives, low molecular monoalkylor dialkyl-amines optionally substituted by OH or SO H groups or the radical of ammonia.

Among the compounds of Formula VI the following may be mentioned: 2.4.6-trichloroor 2.4.6-tribromopyrimidine, 2.4.6-trichloroor 2.4.6-tribromo-5-methyl-, -5- ethyl-, -5-carboxyor -5-carboxymethyl-pyrimidine, 2,4,6- trichloro 5 brornopyrimidine, 2.4.5.6 tetrachloroor 2.4.5.G-tetrabromopyrimidine.

The introduction of a cyanuric radical is best carried out in an aqueous medium at about 0 C. ad at weakly acidreaction, e.g. at a pH value of 3 to 5. Cyanuric halide is used as such in solid form or in solution in an organic solvent, e.g. acetone. In the case of the primary condensation products of a cyanuric halide it is best to choose a temperature of to 60 C. and a pH value of 4 to 6, while for the di-, triand tetrahalogenopyrimidines temperatures between and 100 C. and pH-values from 3 to 7 are most suitable.

The introduction of a monohalogeno-1.3.5-triazinyl radical can also be carried out indirectly by condensing first the amino-monoazo dyestuff with a cyanuric halide and then reacting the obtained 4.6-dihalogeno-l.3.5-triazinyl-Z-amino-monoazo dyestutf with ammonia, a primary or secondary amine.

The diazotization of the mines of Formula III or IV is carried out by the direct or, preferably, the indirect method at temperatures of e.g. 0 to 5 C. The coupling reaction is conducted in a weakly acid, neutral or alkaline medium, preferably atpH 6 to 10, and at low temperatures, e.g. 5 to 10 C.

Examples of coupling components B-H which are suitable for the process are: e.g. l-phenyl-3-rnethyl-5-pyrazolone-2.5-disulfonic acid, l-phenyl-3-methyl-5-pyrazolone 2',4' disulfonic acid, 1-(2'.5-dichloro)-phenyl-3- methyl-5-pyrazolone-4-sulfonic acid, 1-phenyl-3-methyl- 5-pyrazolone-4-su1fonic acid, 1-phenyl-3-methyl-5-pyrazo.-lone-3-sulfonic acid, 1-(2-chloro -phenyl-3-methyl-5- pyrazolone-4- or -5-sulfonic acid, 1-phenyl-3-carboxy-5- pyrazolone-3'- or 4'-sulfonic acid, hydroxynaphthalenesulfonic acids, such as 1-hydroxynaphthalene-4- or -5- sulfonic acid, 2-hydroxynaphthalene-4-, -5-, -6-, -7- or -8- sulfonic acid, l-hydroxynaphthalene-3,6-, -3,8-, -4,7- or -4,8-disulfonic acid, 2-hydroxynaphthalene-3,6- or -6,8- disulfonic acid, l-hydroxyand Z-hydroxynaphthalene- 3.6.8-trisulfonic acid and their mixtures, N-substituted 2- aminoor 3-amino-5-hydroxynaphthalene-7-sulfonic acid or N-substituted 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid e.g. l-acetylamino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, l-chloroacetyl-aminoor 1-,6-chloropropionylamino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1-(4,6-dichloro-1',3',5-triazinyl-2)- amino-8-hydroXynaphthalene-3,6- or -4,6-disulfonic acid, 2-(4-phenylamino-6-chlorol.3.5-triazinyl2) amino- S-hydroxynaphthalene-7,4-disulfonic acid, 2-chloroacetylamino-8-hydroxynaphthalene-6-sulfonic acid, etc.

The diazo components employed in the second mode of operation of the process, namely 2-amino-6-nitroor -6- acylamino- (e.g. -6-acetylamino-, -6-benzoylamino-, -6- oxalylaminoor -6-carbethoxyamino)-naphthalene-4.8-disulfonic acids, are diazotized in the same Way, and the diazo compound coupled with a coupling component conforming to the invention in the same way as in the case of the monocondensation products of a 2,6-diaminonaphthalene-4,8-disulfonic acid and a reactive compound of the Formula V or VI.

Subsequently the nitro group is reduced, e.g. by treatment with an aqueous solution of sodium sulfide or sodium hydrogensulfide, preferably at 60 to 90 C., or the acylamino group is hydrolyzed, e.g. by dissolving the product in 10 to 20 times its amount of concentrated sulfuric acid and diluting with water to a sulfuric acid concentration of about 80% so that the temperature increases to about 100 C., or by heating in an aqueous solution of alkali-metal hydroxides, preferably in a 5% to 10% solution of sodium or potassium hydroxide at 100 C.

The aminoazo compound thus obtained is condensed with a reactive compound of the Formula V or VI as described in the foregoing. On completion of condensation or coupling the solution or suspension may be neutralized with sodium or potassium chloride if desired and the final reactive dyestufi is then salted out or precipitated with acid and subsequently filtered with suction, washed and dried.

In cases where the oxidizing-coppering treatment is carried out the process of British Patents 660,447 and 721,495 may be adopted, but the preferred process is that described in Examples 1 and 4 to 10 of British Patent 660,447 using a water-soluble copper salt and hydrogen peroxide at temperatures ranging from 20 to C.

The copper complex dyestuffs are precipitated from their solutions by salts (sodium chloride, potassium chloride etc.); they are then filtered off, washed if desired and dried.

The new reactive monoazo dyestuffs as well as the copper-containing reactive monoazo dyestuffs obtained from them by simultaneous oxidation and coppering bear three to five sulfonic acid groups and possess therefore good solubility in water, good stability in printing pastes and padding liquors, good compatibility with salts and hard water, good reactivity with vegetable fibers, e.g.

cotton and linen; regenerated cellulose, e.g. viscose filament fibers, viscose staple fibers, cuprammonium rayon, animal fibers, such as wool and silk and synthetic polyamide fibers such as nylon 66, nylon 6 and nylon 11; they are practically insensitive to heavy metal ions such as copper, iron and chromium ions and reserve cellulose-2V2- and triacetate, polyester fibers such as polyethylene terephthalate, polyvinyl chloride and polyvinyl acetate fibers, polyacrylonitrile fibers and polyalkylene fibers such as polyethylene and polypropylene fibers.

The new dyestuffs are suitable for dyeing leather; for dyeing, padding and printing wool and silk, synthetic polyamide fibers, fibers of natural and regenerated cellulose and blends of these fibers. The commonly used padding and printing techniques can be applied, e.g. the padding processes Pad Jig, Pad Steam, Pad Roll, Pad Batch and thermofixation process, and the printing processes named roller printing, screen printing, emulsion printing and Vigoureux printing; in these printing processes the dyestuffs are fixed on the substrate by steaming or thermofixation.

The optimum conditions of application vary with the fiber to be dyed and the dyestuffs used. Animal fibers and synthetic polyamide fibers are best dyed or printed or fixed in acid, neutral or weakly alkaline medium, e.g. in presence of acetic acid, formic acid, sulfuric acid, ammonium sulfate, sodium metaphosphate etc. The dyestuffs can also be applied from an acetic acid to neutral bath in presence of levelling agents, e.g. polyoxyethylated fatty amines or mixtures of these and alkylpolyglycol ethers, in which case the bath is made neutral or weakly alkaline at the end of the dyeing process by the addition of small amounts of an agent of alkaline reaction, e.g. ammonia, sodium bicarbonate etc. or compounds which react alkaline on heating, e.g. hexamethylene-tetramine or urea. Subsequently the goods are thoroughly rinsed and, if necessary, soured with a little acetic acid.

The dyeing, padding and rinting or fixation of the dyestuffs on cellulosic fibers are carried out advantageously in alkaline medium, e.g. in presence of sodium carbonate or bicarbonate, sodium hydroxide solution, potassium hydroxide solution, sodium metasilicate, sodium borate, trisodium phosphate, ammonia etc. To preclude reduction effects in dyeing, padding and printing, it is often advantageous to add a mild oxidizing agent, e.g. sodium l-nitrobenzene-3sulfonate. Dyeings and prints of the dyestuffs on cellulosic fibers are normally fixed by heat treatments. The dyestuffs can also be fixed at low temperatures, e.g. 20 to 40 C., e.g. with an alkali metal carbonate or bicarbonate (sodium or potassium carbonate or bicarbonate) in the case of the dyestuffs bearing a 4.6-dihalogeno-1.3.5- triazinyl-2 group, or with strong alkalis such as sodium or potassium hydroxide, sodium metasilicate or trisodium phosphate, in the case of the dyestuffs bearing a monohalogeno-l.3.5-triazinyl, a dihalogenoor trihalgenopyrimidyl group.

In dyeing, padding and printing applications the dyestuffs can be fixed simultaneously and subsequently, in the same or in a fresh bath, if necessary after intermediate drying. When fixation is carried out in a fresh bath it is advisable to include in it a water-soluble salt, e.g. sodium sulfate, to preclude a partial redissolving of the dyestuif in the liquor. After fixation the portion of unreacted dyestuff, i.e. the dyestuff which has not taken part in the chemical reaction with the fiber, must be removed from the dyed or printed material. Owing to the very slight substantivity and the good solubility in water of the new dyestuffs this removal is in general easy and can often be carried out by rinsing with hot water, whereby in case of prints no staining of the unprinted areas appears. Washing at higher temperatures with solutions of soap or of synthetic detergents, e.g. alkylarylsulfonates such as sodium dodecylbenzenesulfonate, alkyl sulfates such as sodium dodecyl, oleyl or cetyl sulfate, optionally sulfated or carboxymethylated alkylpolyglycol, monoor dialkylphenylpolyglycol ethers, although it is seldom necessary, is nevertheless generally employed in routine padding and printing processes in order to obtain perfect prints and dyeings.

The dyeings and prints on cellulosic fibers possess excellent fastness to water, sea water, washing, acid and alkaline perspiration, crocking, ironing and organic solvents (alcohols, ketones, esters, aromatic and aliphatic hydrocarbons which may be halogenated, pyridine and 1:1-pyridine-water-mixture, dimethylformamide, dimethsulfoxide, etc.), these excellent fastness properties being due to the stable chemical linkage formed between the dyestutf molecule and the cellulose molecule. In addition the dyeings and prints are also very fast to acids (cold dilute acetic and tartaric acid), alkali (sodium bicarbonate and carbonate) and peroxides. They further possess good fastness to light, gas fumes and chlorinated swimming pool water and are suitable for anticrease finishing treatments.

The dyeings and prints on wool, silk and synthetic polyamide fibers possess a good fastness to light and excellent fastness properties to washing, water, sea water, milling, acid and alkaline perspiration, crocking, pressing and organic solvents; they are also stable against chlorinated swimming pool water, peroxides, acids (dilute acetic and tartaric acid in the cold), alkali (sodium carbonate and bicarbonate) and gas fumes.

In the following examples the parts and percentages are by weight and the temperatures in degrees Centigrade.

EXAMPLE 1 31.8 parts of 2.6 diaminonaphthalene-4.8 disulfonic acid are dissolved in 300 parts of Water with the addition of 27 parts of 30% sodium hydroxide solution. 19 parts of 2.4.6-trichloro-pyrimidine dissolved in 20 parts of acetone are then added and the mass is maintained at a temperature of 40-50 for 4 hours with stirring and under reflux. The reaction product formed is precipitated in crystalline form. After cooling to 10-12, 40 parts of 30% hydrochloric acid are added so that a mineral acid reaction ensues, and a solution of 7 parts of sodium nitrite in 30 parts of water is added dropwise for diazotization. The resulting suspension of the diazo compound is run into an ice-cold solution of 35 parts of 1-phenyl--3-methyl-5-pyrazolone-2'.4-disulfonic acid and 50 parts of sodium carbonate in 400 parts of water in the course of about 30 minutes.

The monoazo dyestuif formed is precipitated with the aid of sodium chloride, filtered off and dried. A red powder is obtained, which dissolves in water with a yellowred coloration and dyes cotton and fibers of regenerated cellulose in yellow-orange shades of excellent washing fastness.

A padding solution is prepared with 10 parts of the above dyestufi. in 1000 parts of water and 10 parts of sodium carbonate. A cotton fabric is impregnated with this solution, passed between squeeze rollers so that it contains about 70% of its weight of liquor, and dried.

The padded goods are treated in dry heat for about 5 minutes at rinsed with cold and warm water, soaped at the boil for 15 minutes with a 0.050.1% solution of a non-ionic detergent and rinsed. A brilliant yellowish orange dyeing is obtained, which is fixed so stably as to be fast to boiling and to the other wet treatments and is stable to crease-resistant finishes.

A similar dyestutf is obtained when. the 19 parts of 2.4.6-trichloro-pyrimidine in the above example are replaced by 32 parts of 2.4.6-tribromopyrimidine.

EXAMPLE 2 The aqueous suspension of the diazo compound of 36 parts of 2-amino-6-acetylaminonaphthalene-4.8-disulfonic acid, prepared in the normal way, is run in the course of 30 minutes into an ice-cold solution of 35 parts of 1- phenyl-3-rnethyl-5-pyrazolone-2.5'-disulfonic acid and 50 parts of sodium carbonate in 400 parts of water. The

monoazo dyestuff formed is precipitated with common salt and filtered off. The filter residue is dissolved in 250 parts of water at 75-80, and 100 parts of 30% sodium hydroxide solution are added. The mass is maintained at 7580 for about 30 minutes with stirring, whereupon the saponification of the acetylamino group is complete. On cooling, about 80 parts of 30% hydrochloric acid are dropped in to bring the pH value of the solution to 4-5. After the addition of about 22 parts of 2.4.5 .6-tetrachloropyrimidine the mass is stirred for 4 hours at 60-65". By dropping in diluted sodium carbonate solution a constant pH value of between 4 and 5 is maintained. On completion of the reaction the solution is treated with blood charcoal. After filtration, the dyestuff is precipitated from the solution by the addition of sodium chloride, filtered with suction, and the presscake washed with sodium chloride solution and dried. The ground dyestuif is a red powder which dissolves in water with a yellow-red coloration.

A mercerized cotton fabric is printed with a printing paste of the following composition:

Parts of the above dyestuff 30 Parts of urea 100 Parts of water 395 Parts of 4% sodium alginate thickening 450 Parts of sodium 1-nitrobenzene-3-sulfonate Parts of sodium carbonate The print is dried and fixed by steaming for 10 minutes. It is then rinsed in the normal way with cold and hot water, if necessary soaped at the boil, and rinsed again with hot water and cold water. On drying a brilliant yelloworange print is obtained which has excellent fastness to wet treatments and is stable to crease-resistant finishes.

The corresponding dyestuffs obtained by condensation with 40 parts of 2.4.5.6-tetrabromopyrimidine or 26.5 parts of S-bromo-2.4.6-trichloropyrimidine possess similar properties.

EXAMPLE 3 An aqueous suspension of the diazo compound of 35 parts of Z-amino-6-nitronaphthalene-4.8-disulfonic acid is slowly run into a mixture, cooled to 10, of 35 parts of 1- phenyl-3-methyl-5-pyrazolone-2'.5-disulfonic acid and 50 parts of sodium carbonate in 400 parts of water. On completion of coupling the mass is heated to 80, a solution of 40 parts of crystallized sodium sulfide in 100 parts of water added, and the temperature maintained at 80 for 40 minutes. When the nitro group has been completely reduced the reaction mixture is allowed to cool, and then neutralised with concentrated hydrochloric acid to a pH value of 7. The aminoazo dyestutf is then salted out with sodium chloride. After some time the precipitate is filtered ofi? and washed with concentrated sodium chloride solution. The filter residue is then dissolved in 900 parts of water. This solution is slowly run into a suspension of 18 parts of cyanuric chloride in 300 parts of ice and 200 parts of water at 0-5", while a constant weakly acid reaction of the reaction mixture is maintained by the dropwise addition of diluted sodium carbonate solution. On completion of reaction the dyestuff is salted out with sodium chloride and filtered off. The filter residue is dried with vacuum at room temperature. An orangecolored powder is obtained, which dissolves in Water with an orange-red coloration.

When the 18 parts of cyanuric chloride are replaced by 32 parts of cyanuric bromide, a similar dyestuff is obtained. A padding solution is prepared with 10 parts of the above dyestuif in 1000 parts of water and to it are added immediately before use 10 parts of sodium carbonate at room temperature. A cotton fabric is impregnated with this solution, passed between squeeze rollers so that it contains about 70% of its weight of liquor, rolled up on a roller, and wrapped in rubber or plastic sheets to prevent drying. After 3 /2 hours storage at room temperature the goods are rinsed in cold and warm water, soaped at the boil for 15 minutes in a 0.05-0.1% solution of a non-ionic detergent and rinsed. An orange dyeing is obtained, which is fixed so stably as to be fast to boiling and to the other wet treatments and is stable to creaseresistant finishes.

EXAMPLE 4 75.1 parts of sodium 1-phenyl-3-methyl4-(6"-aminonaphthyl-2-azo) 5 pyrazolone 2,5,4",8-tetrasulfonateobtained according to the particulars of Example 3are dissolved in 900 parts of water and the pH value is adjusted to 5. After the addition of 34.3 parts of sodium 2-phenylamino-4.6-dichloro-1.3.5-triazine 3 sulfonate the temperature is raised to 40 and maintained at 40-45 and the pH value between 4 and 6 by the addition of dilute sodium carbonate solution. On completion of reaction the dyestuff is salted out with sodium chloride and filtered off. The filter cake is dried with vacuum at 40. An orange powder is obtained which dissolves in water with an orange-red coloration.

EXAMPLE 5 The condensation product obtained from 71.5 parts of sodium 1 phenyl-3-methyl-4-(6"-aminonaphthyl-2"- azo-5-pyrazolone-2',5,4",8-tetrasulfonate and 18 parts of cyanuric chloride according to the particulars of Example 3 is dissolved in warm water and adjusted to about 1000 parts and a temperature of 40. To the well stirred neutral solution 9.3 parts of aminobenzene are added dropwise and the temperature is maintained at 40-50 and the pH-value at about 5 by the addition of a 20% sodium carbonate solution. When no further alkali is consumed the formed dyestuff is precipitated by the addition of sodium chloride, filtered off with suction, dried and ground to give a yellow powder which dissolves in water with a yellow coloration and dyes cotton and wool in yellow shades fast to light and to wet treatments.

Similarly on condensing 79.5 parts of the dyestuif sodium l phenyl 3-methyl-4-[6" (4",6"-dichloro1, 3',5-triazinyl 2" amino)-naphthyl-2"azo]-5-py razolone-3.4.8-trisulfonate with 17.3 parts of 3-aminobenzene-l-sulfonic acid in aqueous medium at -45 and at a pH value between 4.5 and 5.0, a yellow dyestuff is obtained which dyes wool and cotton in reddish yellow shades fast to light and to wet treatments.

2 parts of the above dystuff, 0.8 part of an oxethylated fatty amine and 0.5 part of an oleypolygly'col ether are dissolved in 5000 parts of water. After the addition of 2 parts of glacial acetic acid the dyebath is heated to 40-50 and 100 parts of prewetted wool are entered. The dyebath is then brought to the boil in 30 minutes and held at the boil for minutes. Then the dyed wool material is removed, rinsed and dried. A level reddish yellow dying fast to wet treatments is obtained.

EXAMPLE 6 41.7 parts of the monosodium salt of 2-amino-6-(4,6'- dichloro-1'.3'.5-triazinyl 2' amino)-naphthalene-4.8- disulfonic acid obtained by mono condensing 2,6-diaminonaphthalene-4,S-disulfonic acid with cyanuric chloride at 0-5 and at a pH-value of 44.5 and isolating from acid medium-are suspended in 400 parts of water and 40 parts of 30% hydrochloric acid. After cooling to 10 a solution of 7 parts sodium nitrite is added dropwise. When the diazotization is completed the diazo suspension is neutralized to Congo at 5-l0 with 20% sodium carbonate solution and then run slowly into an ice cold solution of 35 parts of sodium Z-hydroxy-naphthalene- 3,6-disulfonate in 400 parts of Water, a 20% sodium carbonate solution being added to neutralize the acid formed during the reaction. After the addition of the diazo suspension the coupling mass is made alkaline with sodium carbonate solution and maintained alkaline until the dyestuff formation at 8-12 is completed. The dyestuff is precipitated with sodium chloride, filtered ofi, dried in vacuum at 30 and gorund. It is a red-brown powder which dissolves in water with a red coloration and dyes cotton in red shades fast to light and to wet treatments.

EXAMPLE 7 When the monocondensation product used in Example areas are Perfectly Whlte' 6 is replaced by 63.2 parts of the disodium salt of 2- amino-6-(4'-phenylamino 6' chloro 1',3',5'-triazinyl- 2-amino)-naphthalene-4,8,4 trisulfonic acid-obtained by monocondensing 2,6-diaminonaphthalene-4,8-disulfonic l acid with 2-phenylamine-4,6-dichloro-1,3,5-triazine 4' sulfonic acid at about 40 and at a pH-value of about 5 and isolating the condensation product from acid meand have the formula The print is dried, steamed for minutes at 102, rinsed with cold and with hot Water, soaped for minutes at the boil with a 0.1% soap solution in distilled water, rinsed again and dried. The obtained red print is 5 fast to light and to wet treatments and the unprinted In the following table are listed a number of further dystuffs which were produced according to the invention dium-and the diazo compound is coupled with sodium SiO3H 1-hydroxynaphthalene-3.8-disulfonic acid, a dyestuff with 15 excellent fastness properties is obtained.

Mercerized cotton fabric is printed 'With a printing paste of the composition Parts of the above described dyestuff 30 S0311 Parts of urea 100 Parts of potassium carbonate 20 Parts of 30% sodium hydroxide solution 2 Parts of sodium 3-nitrobenzene-l-sulfonate 10 Parts of 2.5% sodium alginate thickening 450 In the table they are characterized by the symbols R Parts of water 388 and B, the method of production according to Examples 1 to 7 and by the shade of the dyeing on cotton or wool Parts total 1000 in the columns (I) to (IV).

R Radical of B Radical of Shade of dyeing on cotton or Wool Example No. (I) (II) (III) (IV) 8 2.4.5.fi-tetra-ehloropyrimidine 1-phenyl-3-methyl-5-pyrazo1one-2'.4-disulfonicacid 2 Rcddish yellow. 9 do. 1-pl1enyl-3-methyl-5pyrazolone-3.5-disulionic acid 2 Do. 10 do.. 1-phenyl-3-metllyl-5-pyrazo1one-4-sulfonic acid 2 Do. 11 .do 1-(2 -(51-dich1oro)-pheny1-3-meth371 5-pyrazelonc-4-sulfonic 2 Do.

301 1-hydr0xynaphthalene-3.G-disulfonic acid 1 Red. 1-hydroxynaphthalene-4.fi-disulfonic acid. 2 Red. orno- 1-hydroxy-8'acetylamino-naphthalene-3.fi-disulfonic acid... 2 Red. 15 2.4.5.6-tetracl1lorop 1-hydiroxy-8-ch1oroacetylaminonaphthalene-3.G-disullonic 2 Red.

801 2-hydroxynaphthalene-3.6-disu1fonic acid 2 Red. d 2-hydroxynaphthalene-6.8-disulfonic acid 2 Red. 18 2.4.6-tr1ch1oropyrun1 1ne 1-phenyl-3-methyl-5-pyrazolone-2.5-disulionic acid 2 Reddish yellow. 19 -do 1-pheuyl-3-methyl-5-pyrazolone 3sulfonic acid 1 Do. 20 Cyanuricchlomde 1-phenyl-B-methyl-5pyrazolone-4'-su1fonic acid 3 Do. 21 do 1-phenyl-3-Inethyl-5-pyrazolone-3-sulfonic acid 3 Do. 22 .do l-hydroxynaphthalene-3.G-disulfonic acid 3 Red. 23 2.4.G-trichloro-fi-carbwry-pyrimidine- 1-phenyl-3-methyl-5-pyrazolone-2.4-disu1fonic acid 2 Reddish yellow. 24 2.4.6-trich1oro5-methyl-pyrimidine. dc 2 Do. 25 do 2'hydroxyuaththalene3.6-disulfonic acid 2 Red. 26.- 2.45.6-tetrachloropyrimidine 1-(2-ch1orophenyl)-3-methy1-5-pyrazolone-5-sulfonic acid 2 Reddish yellow. 27.- 2.4.6trichl0ro-5ethy1pyrmnd1ne Lphenyl-B-methyl-5-pyrazolonc-2.5-disu lfonic acid. 2 Do. 28 2.4.G-tribromo-fi-mcthylpyrimidine d 2 Do. 29 2-phenylamino-4.G-dichloro-l.3.5-triazme-4-sulfonic 4 Red.

ac 30 2-ethglamino-d.G-dichloro-l.3.5-triazine-2-sulionic 2-acetylarnino-5-hydr0xy-panhthalene-7-sulfonic acid 5 Red.

aci 31 2-carboxymethylamino-4.6-dichloro-1.3.5-triazine ..do 4 Red. 32 2-arnino-4.6-dichloro-l.3.5-triazine. 2propionylamino-8-hydroxy-naphthalcne-B-sulionic acid- 5 Red. 33.. 2.4.6tribromopyrimidine. l-hydroxynaphthalene-B.6.8-trisulfonic acid 2 Red. 34 2.4.6trichloropyrimidiue Z-hydroxynaphthalene3.tdisulfonic acid 2 Red. 35 2.4.5.dtetrabromdpyrimidlne. Z-hydroxynaphthalene-3.6.8-trisulfonic acid. 2 Red. 36 2.4.6-t1i0h101050311)OXyInBiJllYI-QYIlInldll'll-hydroxynaphthalene.S-disulfcnic acid 2 Red. 37 ecarbcity-2,4.fi-tribromopyrimidine 1-(2'-chlorophenyl)-3-methyl-5-pyrazolone-4-sulfonic acid 2 Reddish yellow. 38 2-(t2-hydroxy-propylamino)-4.6-d1chl0r01.3.5- .do 5 Do.

raizine. 39 do 1hydroxy-naphtha1ene-3.ddisulfonic acid. 5 Red. 2-emin0-4.6-dibromo-1.3.5-triazine do 4 Red. 2-n-butylamino-4.6 diehloro-1.3.5-triazine-- -do 5 Red. 2.4.5.6tetrachloropyrimidine ..do 2 Red. Z-ethoxyethylamino-tt.fidichloro-l.3.5-triazine 2-hydroxynaphthalene-4 sulfonic acid.v 5 Red. 44 2-(t4 -m ethylphenyl-amino)-.6-dichloro-l.3.5- Z-hydroxynaphthalene-S.6.8-trisu1fonic ac 5 Red.

I'IBZIDB 45 2-benzylamino-4.6-dichloro1.3.5-triazine ..do 5 Red. 46 2-arnyilam;no-4.6-dichloro-1.3.5-triazine (amyl ..do 5 Red.

IIIIX me 47 2-(2-carboxyphenyl-amino)4.6-dichloro-1.3.5- 2-hydroxynaphthalene-fi-sulfonic acid 7 Red.

triazine 43 2.4.G-trichloropyrimidine .d0 2 Red. 49 2-phcnylamino-4.G-dichloro-L3.5-triezine-2.4- ---do-- 7 Red.

disulionic acid 50 do 1-(2.5-dichlorophenyl)3-methyl-5-pyrazolone-4'- 4 Reddish yellow.

sulfonic acid 51 2-naphthyl-2-amino-4,6-diehloro-l.3.5-triazine 5 3.6-disull'0nic acid 52 2-naflhthyl lfamin0-4.6-dichloro l.3.5-triazine-4'- l-hydroxynaphthalene-4-sulfonic acid 4 Red.

su onic aci 53 2.4.5.fi-tetrachloro-pyrimidine l-hydroxynaphthalenw 7disulfonic acid 2 Red. 54 2-methylamino-4.fi dichloro-l.3.5-triazine do 5 Red. 55.- 2-diethylamino LG-dichloro-l.3.5-triazine 5 Orange. 56 2-di-(3f-hydroxypropyl)-amino-4.6-dichloro 5 Do.

triazme R Radical of B Radical of Shade of dyeing on cotton or wool Example No. (I)

57 2-N-methyl-N-ethyl-amin0-4.6-dichloi0-l.3.5 1-phenyl-B-methy1'5-pyrazolone-3sulfonic acid 4 Rcddish yellow triazine-2-sulfonic acid 58 2-naphthyl-l-an1ino4.6-dichl0rol.3.dtriazinc- -do 4 D0.

4.8-disulionic acid. 59. 2-incthoxy-4.6-dicl1loro-1.3.5-triazinc .do 4 Do.

do 2-hydroxynaphthalene-3.fi-disulionic acid. 4 Red. 61 (4-mctl1ylcyclo-hexylamino)-4.6-dichloro-1.3.5- l-hydroxynaphtl1ale11c-3.6.8-tr1sulfonic acid 5 Red.

triazinc. 62 2-(3-chlorophcnyl-amino)4.6-dichl0ro-1.3.5- ....d 7 Rod.

triazine. 63 2-N-ethyl-N-phenyl-amino-4.6-dichlor0-1.3.5- -do Red.

triazine. 64 2-N-methyl-N-phcnyl-amino-4.G-dichloro-l.3.5- l-phcnyl-B-methyl-5-pyrazolone-2'.5-disulionic aicd 5 Reddish yellow triazine. 65 2-11aphthyl-2-amino-4.6-dichloro-1.3.5-triazine-5- .do 5 Do.

sulfonic acid. 66 2-g4f-carboxyphenyl-amino)-4.6-dichloro-1.3.5- .do 5 Do.

riazine. 67 2-(2-carboxyethyl-amino)-4.6-dich101'o-1.3.5- 1-hycroxy-B-benzoyl-aminonaphthalene-3.6-disulto11ic 4 Red.

triazine. aci 68 2-ethoxy-4.6-dichloro-l .3 .5-triazine 110.. 4 Red. 2-amin0-4.6-r1ichloro-1.3.5-triazine- .do.. 5 Red. 2.4.5.6-tetrachloro-pyrimidine.. l-hydroiy 8 acetylaminonaphthalene5.7 disulfonic acid. 2 Red. 71 do l-hydfoxy-7-propionyl-aminonaphthalene-3.6-disulfonic 2 Red.

acid. 7 5-carboxymetl1yl-2.4.6-trichloropyrimidine .do 2 Red. 73 2-g2f-hydroxyethyl-amino)-4.6-dicl1loro-1.3.5 .....do 5 Red.

nazme. 74 do 1-(2-methyl-6-chlorophcnyl)-3-Inethyl-5-pyraz0lone-4- 5 Reddish yellow snlfonic acid. 75 2-phelnylamino4.odichloro-l.3.5-triazinc-3-sulfonic do 4 Do.

aci 76 2.4.6-tricl1loropyrimidine 0 1 Do. 77 do 1-hydroxy-S-propionylaminonaphthalene-Ii.5-disulfonic 2 Red.

acid. 78 2-cycl0hexyla1nino-4.fi-dichloro-i.3.5-triazine o 5 Red.

. 2-(3-hydroxybutylamino)-4.6-dichloro-1.3.5-triazine 2-l1ydroxynaphthalene-7-sulfonic acid- 5 Red.

2-(3-hydroxypropylamino)-4.6-dichloro-1.3.5-triazine l-hydroxy-7-acetylaminonaphthalene-3-sulfon1c acid. 5 Red 2-(if-rncthoxypropylamino)-4.6-dichlom-1.3.5-tria- .do 5 Red.

zine.

82 2.4.5.(i-tetrachloropyrimidine do 2 Red.

83. .....do 1-hydroxy-S-benzoylaminonaphthalene-3.5-disulfonic aeid 2 Red.

84 Z-DaphthyI-Z-amino4.6-dichloro-l.3.5-triazine- -do 4 Red.

5.7disul.tonic acid.

85 Z-methylamino-i.6-dibromo-1.3.5-triazine .dc 7 5 Red.

87 o 1-phenyl-3-methyl-5-pyrazolone-2.5-disulfonic acid 4 Reddish yellow.

2-(2-hydroxyethylamino)-4.6-dibromo1.3.5-triazine d 5 Do.

. 2-ethylamino-4.G-dichloro-l.3.5-triazine ..do.- 5 Do.

. 2-n propylarnino-4.G-dichloro-I.3.5-triazine l-hydroxy-fi-benzoylaminonaphthalene-B-sulfonic ac1d.- 5 Red. Z-dl-(T-hydroxyeth yl) amino-4.6-dichlor0-l.3.5-triado 4 Red.

zlne.

2.4.5.fi-tetrachloropyrimidine do 2 Red.

....de 1-hydroxy-7-acctylaminonaphthalenc-3.fi-dlsulfonlc acid 2 Red.

2-N-2-hydroxyethyl-N-phenylamin0-4.6-dichloro- .do 5 Rod.

1.3.5-triezine. 2-naphthyl-l-amin0-4.6-dichloro-1.3.5-triazinel-h ydroxy-fi-butyrylaminonaphthalcne-3-sulfonic acid- 7 Red.

3.6-disulfonic acid.

Oyanuric chloride l-hydroxy-s-butyrylaminonaphthalone-3.fi-disulfonic acid. 6 Red.

2-dimethylamino-4.6-dichlor l-hydroxy-S-acetylaminonaphthalene-3.5-disulf0nic acid. 5 Red.

2.4.5.6-tetrachloropyrimidine ...do 2 Red.

Z-di:(2f-hydroxy ropyl)-amino-4.6-dieh1oro 2-hydroxynaphthalenc-5-sulfonlc acid 5 Red.

nazme.

2-11-butoxy-4.6-dichloro-1.3.5-triazine l-hydroxynaphthalene-i.fi-disulfonic acid 4 Red.

2-4.fi-trichloropyrimidine -do 1 Red.

2-ph%iylamino-4.6-dibromo-1.3.5-triazine 4 Red.

aci 5carboxymcthyl-2.4.fi-tribromopyrimidine 2 Red. 2-(4-methoxybutylamino)4.6-dichlor0-1.3. 5 Red. 2-phenylamino-4.6-dichloroL3.5-triazine-2.5-disul- 5 Red.

fonic acid. 106 do l-p 4 Rcddish yellow. 107 N- ethyl-N-carboxymethylamino-4.fi-dichloro- 5 D0.

1.3.5-triazine.

2-(4-carboxyphenyl-amino)-4.6dicl1loro-1.3.5- 5 Do.

triazine.

. -do 1-hydroxynaphthalene-S-sulfonic acid 5 Red.

2-g2;m ethoxyphenyl-amino)-4.6-dichloro-1.3.5- 2-hydroxynaphthalene-3.G-disulfonic acid 5 Red.

riazine.

2-n-pr0poxy-4.6-dicl1loro-1 .3.5-triazine -do 4 Red.

112 2-naphthyl-1'-amino-4.6-dichl0ro-1.3.5-triazinc- 2-hydroxynaphthale 5 Red.

67-sulionic acid.

113 2-naghthyl-2ft-iamino.6-dichl0ro-1.3.5-triazine-6- 1-phenyl-3-carboxy-5-pyrazolone-4-sulfonic acid 5 Orange.

su onic aci 114 2.4.5.fi-tetrachloro-pyrimidine "do 2 Do.

115 2-napht hyl-2-amino-4.6-dichloro-1.3.5-triazinel-hydroxynaphthalene+sulionic acid 4 Red.

4.8-disulf011ic acid.

116 2-naphthyl-2-amino-4.6-dichloro-1.3.5-triazine- .-do 7 Red.

5'.7-disulfonic acid.

117 2-phenylamino-4.fi-dichloro-l.3.5-triazine-2.4- do 5 Red.

disuli'onic acid.

118 do 1-hydroxy-7-benzoylaminonaphthalene-3-sulfonic acid. 4 Red.

119 Cyanuric chloride 1-hydroxynaphthalene-4.7-disulfonic acid 6 Red.

1 (III)=i\Iethod of production according to example.

EXAMPLE 120 fate and 28 parts of crystallized sodium acetate in 200 90 parts of the dyestuif (Mol. Wt. 898 as the tetra so- 70 parts of Water is added. 80 parts of 10% hydrogen perdium salt)obtained by coupling 2-diazo-6-(2'.6'-dioxide solution are then added dropwise in 60 minutes at a chloropyrimidy1-4'-amino)naphthalene-4.8-disulf0nic acid temperature of 3035. The pH-value is maintained at with 1 phenyl 3 methyl 5 pyrazolone-Z.4-disulfonic 4.8-5 .2 by drop wise addition of a 25% ammonia solution. acid are dissolved in 1500 parts of Water and to this The color of the solution changes from yellow to red. solution a solution of 27 parts of crystallized copper sul- 75 On stirring for further 30 minutes the yellow dyestuff 13 14 disappears and coppering is complete. The copper complex Parts of the dyestuff obtained according to the pardyestuff formed is precipitated with sodium chloride, ticulars given above 60 filtered off and dried. A red powder is obtained which dis- Parts of urea 200 solves in water with a red coloration. When a spun rayon Parts of water 535 fabric is printed with this dyestufl' according to the method Parts of 3% Sodium alginnte thickening 200 described in Example 2, a red print of good light and wet Parts of a highly Sulfonated Castor Oil 5 fasteness is obtained. Dyestuffs with similar properties were obtained by replacing l-phenyl-3-methyl-5-pyrazo- Parts total 1000 ne-2'-4'-diSn1f0nie acid y One Of the following Coupling 10 The printed slubbing is steamed for two 45-minute components: periods with intermediate cooling. It is then rinsed with Shade of the Example dyeing on No. Coupling component cotton 121 1-phenyl-3-mcthyl-5-pyraz0lone-2.5-disu1lonic acid r. Red. 122 .t 1-phenyl-3-mcthyl 5-pyrazolone-4-sulionic acid Red. 123 l-hydroxynaphthalene-3.6.8-trisulfonic acid Blue. 124 2hydr0xynaphthalene-Ii.6.8-trisu1f011ic acid Reddish blue. 125.. 2-hydroxynaphtha1ene-5.8-disulfonic acid. Do. 126 2-11ydroxynaphthalene-b.7-disulfonic acid-" Do.

' Blue.

EXAMPLE 129 hot and with cold water and dried. The obtained navy blue print is fast to light and to wet treatments.

31.8 parts of 2.6-diaminonaphthalene-4.8-disulfon1c acid FOr printing cotton ths f ll i procedure is Suitable; are dissolved in 300 parts of water with the addition of 30 Mgrcerized cotton Sateen i printed with a paste f h parts of sodium hydroxide solution. 23 parts of f ll i composition; 2.4.5.6tetrachloropyrimidine dissolved in 100 parts of acetone are added with good stirring, and the mass stirred Parts of the above dyestufi 50 under reflux for 20 hours at a temperature of 50. At Parts of urea 100 the same time the pH value of the solution is maintained 30 Parts of Water 375 at 4.5-5.5 by the dropwise addition of dilute sodium car- Parts of 3% SOdnlln alglnaie thlekenlng 450 bonate solution. The reaction product thus formed gradu- Parts sodnlIn 3'nitFObenZene-lrsnlfonate 10 ally precipitates in crystalline form. After approximately Part5 calclned Sodlum Carbonate 15 90% of the diamino compound has reacted, the mass is made alkaline by the addition of about 60 parts of 20% Parts total 1000 sodium carbonate solution to give an alkaline reaction on The print is dried, steamed for minutes at 102, Brllllnnt Yellow {ndleator P pe P )Nhleh the gTea'ter rinsed in cold and in warm water, soaped at the boil, P of the preelpltate g Into selutlon- The $011190? rinsed again and dried. It is of a navy blue shade posis filtered free from the msoluble residue and the filter 1s shssing excellent light and Wet fasmess' Washed With The PP Product i precipitafed 40 The dyestuff can also be fixed on the fiber by treatment from e filtrate y the addltlon of Sodluln chlorlde in dry heat for about 5 minutes at 140 -1SO or for about filtered oil and stirred into 300 parts of water at 0. 40 1 minute at 200 Parts of 30% hydrochloric acid are edded to give a Since the dyestuff is practically non substantive and well Strongly acid reaction 011 Congn Red indleator Paper-Then soluble in water, the non fixed portion can also be rea solution of about 5.5 parts of sodium nitrite in 20 parts moved in the f ll i manner; of water is added dropwise to the suspension at O-5. To The fi d Print i Washed f r 5 minutes i ld water the resulting suspension of the diazo compound is added at a goods to hquor ratio f 1:40 h put into a new an i -601d a a Solution of 33 Parts Of Y Y' cold water bath (goods-to-liquor ratio 1:40) which is naphthalene-3.6.8-trisulfonic acid and parts of sodium heated to 100 i the course of 5 minutes and held at carbonate in 300 Parts of Water- The red monoalo 5O 100 for 5 minutes. The washed print is withdrawn, stuff formed is precipitated with common salt and filtered rinsed with running tap Water and dried. h navy blue olf. print is fast to light and to wet treatments and the un- An amount of the filter cake equivalent to 90 parts of i t d area is perfectly white. 100% free acid monoazo dyestuff (mol. wt. 894) is dissolved in water and the oxidizing-coppering process is EXAMPLE 130 carried out as described in Example 120. After precipita- 76,3 parts f the monoazo dyestuff (mol. wt. 763 as tion and drying a dark powder is obtained which dissolves the tetra sodium salt)obtained by alkaline coupling of in Water with a blue coloration. diazotized 2 amino-6 acetylaminonaphthalene 4.8- A cotton fabric is impregnated with a solution containdi l l a With l-hydroXynaphthelene disuling fonic acid-is simultaneously oxidized and coppered according to the method described in Example 120. The 3 Parts of the above dyeetufi, dyestuff obtained is stirred into 700 parts of a 5% sodium 20 parts of urea, hydroxide solution and maintained at -90 until saponi- 2 parts of sodium carbonate, and fication of the acetylamino group is complete. The soluparts of water 5 tion is then neutralized with about 80 parts of 30% hydrochloric acid and allowed to cool. The copper-complex dyestutf is completely precipitated with sodium chloride, filtered oif and washed with sodium chloride solution. The moist filter cake is stirred into 800 parts of 7 hot water, and solved at a pH value of 5-6, then 20 pressed between squeeze rollers so that it contains 70% of its weight of liquor, and dried. It is then treated for 4-5 minutes in dry heat at rinsed in cold and warm water, soaped at the boil for 15 minutes with a 0.2% solutionof a non-ionic detergent and rins A y blue y parts of 2.4.5.6-tetrachloropyrimidine are added and the 111g 18 ebtalned Whleh fixed $0 stably as to be fast to temperatur maintained at 70 with stirring until no fursoda bolling and to the other wet treatments. ther free amino group is indicated. The: reaction mixture For the Vigoureux or melange printing of wool a paste is kept at a constant pH value of 5.5 during this time of the following composition is used: 75 by the dropwise addition of dilute sodium carbonate 15 solution. On completion of condensation the dyestulf is precipitated with sodium chloride and then filtered off. The dried and ground dyestuff is a dark powder which dissolves in water with a blue coloration.

Cotton is dyed according to the method described in Example 1. A reddish-blue dyeing is obtained, which is fixed so stably so as to be fast to soda boiling and to the other wet treatments.

EXAMPLE 13 l 80 parts of the aminomonoazo dyestulf (as the tetrasodium salt)obtained by alkaline coupling of diazotized 2 amino 6 acetylaminonaphthalene 4.8 disulfonic acid with 1 hydroxynaphthalene 3.6.8 trisulfonic acid and subsequent caustic-alkaline saponificationare dissolved in 800 parts of water and the pH value is adjusted to 6-7 by means of sodium carbonate. In 2 hours the solution is added to an ice'cold suspension of 20 parts of cyanuric chloride in 100 parts of water. The pH value is maintained at 4-5 by the addition of 20% sodium carbonate solution. The suspension is stirred at until no further aminoazo dyestutf is present, heated to 20, and oxidizing-coppering then carried out by the method described in Example 120. After precipitation and drying a dark powder is obtained, which dissolves in water with a blue coloration.

The dyestulf is applied to a cotton fabric by the method described in Exampl 3 to give a blue dyeing fast to boiling.

An alternative padding method is as follows: 100 parts of a fabric of viscose staple fiber are padded at room temperature with an aqueous neutral solution of 50 g./l. of the above dyestulf, squeezed to about 180% of its original dry weight and dried. Th dyeing is then developed and fixed by treatment for about 90 minutes in a bath at 40-50 (goods-to-liquor ratio 1:50) containing 250 g./l. of calcined sodium sulfate, 2 g./l. of sodium 3- nitrobenzene-l-sulfonate and g./l. of sodium bicarbonate. It is then rinsed in cold and in hot water, soaped at the boil for 10 minutes in a 0.3% soap solution in distilled water, rinsed again and dried. The obtained navy blue dyeing is fast to light and to wet treatments.

For printing cotton the following procedure is suitable: Cotton cretonne is printed with a paste of the composition:

Parts of the above dyestuif 50 Parts of urea 100 Parts of sodium 3-nitrobenzene-l-sulfonate 10 Parts of sodium bicarbonate Parts of a 3% sodium alginate thickening 450 Parts of water 375 Parts total 1000 The print is dried at 50, fixed by steaming for 10 minutes at 102 and finished as described in the last paragraph of Example 129. The obtained navy blue print is fast to light and to wet treatments and the unprinted area is perfectly White.

EXAMPLE 132 The dyestuif solution obtained by the procedure given in Example 131 is heated to 40 immediately after the condensation with cyanuric chloride, and then 10 parts of aminobenzene are added. The mixture is stirred for 4 hours, while a constant pH value of about 7 is maintained by the addition of sodium carbonate solution. On completion of the second condensation the oxidizing-coppering treatment is carried out according to the method described in Example 120. After precipitation and drying a dark powder is obtained which dissolves in water with a blue coloration. A cotton fabric is dyed according to the procedure given in Example 7. A blue dyeing is obtained, which is fixed so stably as to be fast to soda boiling and to the other wet treatments.

EXAMPLE l3 3 72.1 parts of the monoazo dyestulf sodium 1 hydroxy 2 (6' aminonaphthyl 2 azo) naphthalene- 3.6.4.8' trisulfonateobtained from 2- diazo 6- nitronaphthalene 4.8 disulfonic acid and 1 hydroxynaphthalene-3.6-disulfonic acid according to the procedure described in Example 3are dissolved in 900 parts of water at 40 and the pH value is adjusted to 5. 34.3 parts of sodium 2 phenylamino 4.6 dichloro 1.3.5- triazine-3'-sulfonat in the form of a concentrated aqueous solution are added; the temperature is maintained at 40-45 and the pH-value at 56, a sodium carbonate solution being dropped in for neutralizing the acid formed during the reaction. On completion of the condensation the dyestuff is salted outwith sodium chloride, filtered off, brought again into solution and simultaneously oxidized and coppered at 35 by means of copper sulfate and hydrogen peroxide in the presence of sodium acetate as buffer for maintaining a pH-value of 5-5.5 throughout the reaction. The dyestuff is isolated by salting out and filtering, dried and ground, it is then a dark powder soluble in water with a dark blue coloration.

Pad Batch dyeing process: Mercerized cotton sateen is impregnated at 25 with a padding liquor containing per liter:

50 grams of the above dyestufl 150 grams of calcined sodium sulfate 30 grams of sodium metasilicate 20 grams of a 30% sodium hydroxide solution.

The impregnated material is squeezed so that the pickup of liquor is about of the dry weight, Wrapped in a sheet of plastic (e.g. polyethylene) and stored for about 24 hours at 25 It is then rinsed with cold and with warm water, soaped at the boil for 15 minutes with a solution containing 0.5 gram of a carboxy methylated or sulfated alkylpolyglycol ether and 0.5 gram of sodium carbonate per liter, rinsed again and dried. The obtained navy blue dyeing is fast to light and to wet treatments.

In the following table are listed further copper complex dyestuffs which were obtained by the oxidizingcoppe'ring treatment of metal-free dyestuffs disclosed in the foregoing Examples 1 to 119. The method employed was that described in Example 120. In the table the dyestuffs are characterized by the example number of the metal-free dyestuffs and by the shade of the dyeing on cotton.

Oxidizedcoppered dyestnlf of Example Shade of dyeing on cotton Example No.:

The following table contains some copper complex 3531 Shade of dyestulfs of the formula dyestufi dyeing on of Example cotton 52 Blue. H0 8 O-Cu-0 53 Do. I 54 Do. IL L 57 Red. =N.. 58 Rod. 60 Blue. 61 D0. RHN-- 62 Do. 63 Do. 64 Red. SO H 66 Red. 67 Blue. at s"- 0- 72 Do. g2 38: which were obtained according to the details given in 77 Do. Examples 129 and 133 and are characterized by the reacgi 1 3: tivecomponent from which R is derived (Column I), by 86 Do. the coupling component from which 87 Red. 88 Red. 89 Red. ,0 93 Blue. 95 Do: l 9 Do. 8% gt 0. 100 1s derived (Column II), by the method of preparation 101 used (according to the example mentioned in Column 102 Do. g Bo. III) and by the shade of the dyelng on cotton (Col-urrm 0. 106 Red. IV) 1% In Examples 211, 214, 216, 219 and 220 the final con- 111 densation with the reactive components mentioned in gg- Column (I) was carried out under the same conditions 116 Do: as described in Example 133. fig 38' In Example 212 the cyanuric bromide was condensed 119 Do- 'with the copper-containing aminomonoazo dyestuff in the same manner as described in Example 131.

Shade of 0 dye- =Rad1ca1ot ing on R= Radical of -B cotton Example No. (I) (II) (III)! (IV) 209 2.4.5.6tetrach10ropyrimidine l-hydroxy-S-acetylaminonaphtha1ene-3.6-disulfonie acid Blue. 210 Z-amino'4.6-dlch1oro-1.3.5-triazine o 133 Do. 211 do 1-hydroxynaphthalene-3.6.8-tr1sulfonic ac1d...- 130 Do. 212 Cyanuric bromide o -do 130 Do. 213 2.4.5.6-tetrachloropyrimidine 2-hydroxynaphthalene-3.6.8 trisulfonic acid 130 D0- 214 2-methoxy-4.6-dichlor 0-1.3.5-triazinev- 1'hydroxy-fS-acetylaminonaphthalenei 5disulfonlc acid 130 Do. 215 do 1-hydroxynaphthalene-4.6-dlsulfonic acid 133 Do. 2-(2-hydroxyethylamino)-4.6-dichloro-1.3 triazined 130 Do. 217 .410 132 Do. 218 2.4.6'trichloropyrimidine 130 D0. 219 2amino4.6-dichloro-1.3.5-triazlne 130 Do. 220 2-methylamino-4.6-dichlor0-1.3.5-triazine 130 Do.

1 (III)=Meth0d according to.

Formulae of representative dyes of the foregoing examples are as follows:

23 24 References Cited FOREIGN PATENTS AT NT 1,221,621 1/1960 France. UNITED STATES P E S 1,246,743 10/1960 France. 2,951,071 8/1960 Tilley 260-153 1,241,551 8/1960 France. 3,157,630 11/1964 Stephen et a1. 260-146 5 1,225,281 2/19(0 France- 3,268,505 8/1966 Schundehutte et a1. 260-446 FLOYD HIGEL, Primary Examiner 333223 1211333 551???? "566 1215;

1C 6 e a a 9 1 2 2,943,085 6/1960 Oesterlein 260146 8 5 60 

1. A MONOAZO DYESTUFF OF THE FORMULA 